Ethyl Acetate → HCID 67136046, compound

HRID 230930Notes

Reaction equation

HRID 230930 reaction equation
[C:1]([C:3]1[C:4]2[C:11]([O:12][CH3:13])=[CH:10][CH:9]=[CH:8][C:5]=2[S:6][CH:7]=1)#[CH:2].I[C:15]1[CH:23]=[CH:22][C:18]([C:19]([OH:21])=[O:20])=[CH:17][CH:16]=1.C(OCC)(=O)C>C(N(CC)CC)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cu]I>[C:19]([C:18]1[CH:22]=[CH:23][C:15]([C:2]#[C:1][C:3]2[C:4]3[C:11]([O:12][CH3:13])=[CH:10][CH:9]=[CH:8][C:5]=3[S:6][CH:7]=2)=[CH:16][CH:17]=1)([OH:21])=[O:20]

Participants

7

Reactant 3

HCID 8857Ethyl AcetateHCID 120854-Iodobenzoic acidHCID 23103561HCID 23103561, compound

Product 1

HCID 67136046HCID 67136046, compoundYield 97.7%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

3-Ethynyl-4-methoxybenzo[b]thiophene (0.2 g) was dissolved in triethylamine (4mL). To the solution were added 4-iodobenzoic acid (0.29 g), tetrakis(triphenylphosphine)palladium (0) (0.12 g) and copper (I) iodide (41 mg), and the mixture was heated for ref lux under an argon atmosphere overnight. The reaction mixture was poured into ethyl acetate-1 mol/L hydrochloric acid, and the insoluble material was removed by filtration. The organic layer was separated from the filtrate, washed with water and brine. The organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=1/1-1/2) to give 3-[2-(4-carboxyphenyl)ethynyl]-4-methoxybenzo[b]thiophene (0.32 g). This material was dissolved in N,N-dimethylformamide (10 mL). To the solution were added potassium carbonate (0.29 g) and benzyl bromide (0.16 mL), and the mixture was stirred at room temperature for three hours. The reaction mixture was poured into water, and the resulting mixture was extracted with diethylether. The extract was washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=10/1) to give the title compound (0.2 g).

Workup

  1. temperaturethe mixture was heated for ref lux under an argon atmosphere overnight
  2. customthe insoluble material was removed by filtration
  3. customThe organic layer was separated from the filtrate
  4. washwashed with water and brine
  5. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  6. customthe solvent was removed under reduced pressure
  7. customthe residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=1/1-1/2)

Sources & evidence

ORD record
ord-2ac924aa99bf4fdc8e429fc99a194bf1
Source dataset
uspto-grants-2009_07
Patent number
US07566699B2

Reaction notes

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